Abstract
The regularities of the reaction of N,N′-diphenyl-1,4-benzoquinone diimine with thiophenol in chlorobenzene at 343 K were studied by kinetic spectrophotometry. The reaction orders were determined for the components under the conditions when the concentration of thiophenol considerably exceeded that of quinone diimine: n QDI = 1.5 for quinone diimine and n PhSH = 1.0 for thiophenol. The initiators (azo-bis-isobutyronitrile and tetraphenylhydrazine) were found to considerably accelerate the reaction, which suggests that the reaction proceeded by the chain mechanism. The reaction chain length changed from one dozen to several dozens of units depending on the experimental conditions. The chain mechanism (kinetic scheme) of the reaction was suggested; it agrees with the experimental data, according to which the chains are initiated simultaneously by the second and third order reactions between quinone diimine and thiophenol. The rate constants of these stages at 343 K were determined: k bi = 0.014 ± 0.002 L mol−1s−1; k tri = 22.8 ± 1.8 L2 mol−2s−1. The limiting stage of chain propagation was concluded to be the reaction of the thiyl radical with quinone diimine; the rate constant of this stage was evaluated: k pr ∼ 1.3 × 106 L mol−1 s−1 at 343 K.
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References
The Chemistry of the Quinoid Compounds, Ed. by S. Patai (Wiley, London, New York, Sydney, Toronto, 1974), Vol. 1, Parts 1, 2.
The Chemistry of the Quinoid Compounds, Ed. by S. Patai and Z. Ruppoport (Wiley, Chichester, New York, Brisbane, Toronto, Singapore, 1988), Vol. 2, Parts 1, 2.
A. A. Kutyrev and V. V. Moskva, Russ. Chem. Rev. 60, 72 (1991).
S. Lu, W.-W. Li, D. Rotem, et al., Nature Chem. 2, 921 (2010).
E. T. Denisov and I. B. Afanas’ev, Oxidation and Antioxidants in Organic Chemistry and Biology (Taylor and Francis, 2005).
V. T. Varlamov, Dokl. Akad. Nauk SSSR 332, 457 (1993).
V. T. Varlamov, Kinet. Catal. 42, 759 (2001).
S. Ya. Gadomsky and V. T. Varlamov, Kinet. Catal. 50, 348 (2009).
A. V. Gadomskaya and V. T. Varlamov, Dokl. Phys. Chem. 439(Part 2), 150 (2011).
J. M. Snell and A. Weissberger, J. Am. Chem. Soc. 61, 450 (1939).
G. B. Afanas’eva, E. V. Tsoi, O. N. Chupakhin, et al., Zh. Org. Khim. 21, 1926 (1985).
A. V. Gadomska, S. Ya. Gadomsky, and V. T. Varlamov, Kinet. Catal. 53, 525 (2012).
F. Ignatz-Hoover and B. H. To, Rubber World 230(5), 22 (2004).
O. W. Maender, C. J. Rostek, A. R. Katritzky, et al., US Patent No. 7718722 (2010).
K. B. Piotrovskii and Z. N. Tarasova, Ageing and Stabilization of Synthetic Rubbers and Curing Agents (Khimiya, Moscow, 1980).
Y. Kumagai, J. Health Sci. 55, 887 (2009).
M. Liebeke, D. C. Pother, N. van Duy, et al., Mol. Microbiol. 69, 1513 (2008).
Methods in Enzymology, Vols. 378, 382, Ed. by H. Sies and L. Packer (Elsevier Academic, San Diego, London, 2004).
A. V. Antonov, S. Ya. Gadomsky, and V. T. Varlamov, Russ. Chem. Bull. 55, 1723 (2006).
S. Ya. Gadomsky and V. T. Varlamov, Russ. Chem. Bull. 56, 2376 (2007).
A. L. Aleksandrov and L. D. Krisanova, Bull. Acad. Sci. USSR, Chem. Sci. 29, 1735 (1980).
S. W. Benson, The Foundations of Chemical Kinetics (McGraw-Hill, New York, Toronto, London, 1960).
E. T. Denisov, Mechanism of Homolytic Decay of Molecules in Liquid Phase, Results of Science and Engineering, Ser. KiK (VINITI, Moscow, 1981), Vol. 9 [in Russian].
C. Walling and W. Helmreich, J. Am. Chem. Soc. 81, 1144 (1959).
O. Turunc and M. A. R. T. Meier, Eur. J. Lipid Sci. Technol. 115, 41 (2013).
J. Butler and B. M. Hoey, Free Radical Biol. Med. 12, 337 (1992).
O. Ito, K. Nogami, and M. Matsuda, J. Phys. Chem. 85, 1365 (1981).
O. Ito, in The Chemistry of Free Radicals. S-Centered Radicals, Ed. by Z. B. Alfassi (Wiley, Chichester, New York, Weinheim, Brisbane, Singapore, Toronto, 1999), Ch. 6.
C. Chatgilialoglu, A. Altieri, and H. Fischer, J. Am. Chem. Soc. 124, 12816 (2002).
C. Chatgilialoglu and K.-D. Asmus, Sulfur-Centered Reactive Intermediaties in Chemistry and Biology, NATO ASI Ser. A: Life and Sience (Plenum, New York, 1990), Vol. 197, p. 327.
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Original Russian Text © V.T. Varlamov, A.V. Gadomska, 2015, published in Zhurnal Fizicheskoi Khimii, 2015, Vol. 89, No. 4, pp. 629–637.
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Varlamov, V.T., Gadomska, A.V. Kinetics and mechanism of the chain reaction of N,N′-diphenyl-1,4-benzoquinone diimine with thiophenol in chlorobenzene. Russ. J. Phys. Chem. 89, 616–623 (2015). https://doi.org/10.1134/S0036024415040275
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DOI: https://doi.org/10.1134/S0036024415040275